CN107137358A - A kind of liquid metal drug system and its preparation and delivering, method for releasing - Google Patents
A kind of liquid metal drug system and its preparation and delivering, method for releasing Download PDFInfo
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- CN107137358A CN107137358A CN201710347292.XA CN201710347292A CN107137358A CN 107137358 A CN107137358 A CN 107137358A CN 201710347292 A CN201710347292 A CN 201710347292A CN 107137358 A CN107137358 A CN 107137358A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/02—Inorganic compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/0002—Galenical forms characterised by the drug release technique; Application systems commanded by energy
- A61K9/0009—Galenical forms characterised by the drug release technique; Application systems commanded by energy involving or responsive to electricity, magnetism or acoustic waves; Galenical aspects of sonophoresis, iontophoresis, electroporation or electroosmosis
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
- A61K9/16—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction
- A61K9/167—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction with an outer layer or coating comprising drug; with chemically bound drugs or non-active substances on their surface
- A61K9/1676—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction with an outer layer or coating comprising drug; with chemically bound drugs or non-active substances on their surface having a drug-free core with discrete complete coating layer containing drug
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Abstract
A kind of liquid metal drug system, including liquid metal and it is coated on the drug powder of liquid metal droplet outer surface, present invention also offers the preparation method of the liquid metal drug system, liquid metal is added in glass beaker, add the medicine of corresponding proportion, it is stirred at a certain temperature with certain rotating speed using agitator, liquid metal aoxidizes to form oxide-film in atmosphere, drug powder is coated on oxide-film；The liquid metal of the coating medicine is put into close Hank ' the s solution or HCl solution of physiological solution, human body fluid composition, electrode is added at solution two ends, be passed through certain voltage, the liquid metal miniature droplets of coating medicine can free movement forward, realize the medicine delivery of liquid metal；After the liquid metal that negative electrode contacts the coating medicine carries out electro photoluminescence, the liquid metal can slowly carry out insoluble drug release；The present invention can easily and fast, efficiently realize the load, delivering and release of liquid metal medicine.
Description
Technical field
The invention belongs to Drug delivery technology field, more particularly to a kind of liquid metal drug system and its preparation and pass
Give, method for releasing.
Background technology
Cancer is the first big disease killer of nature, and chemical drug treatment is important treatment means, but its can produce it is various
Side effect, and targeting is low, and utilization rate is low etc..Drug delivery system (Drug delivery system, DDS) can with gram
The shortcoming of above-mentioned chemical drug treatment is taken, therefore is always industrial quarters and the research emphasis of academia, development low-cost high-efficiency medicine is passed
The new technology sent has great social value and extensive market prospects.
The substance system of carrying medicament is varied, and existing research at present includes liposome, polymer micelle, tree-like height
Molecule, protein, cell, bacterium, graphene, mesoporous silicon, hydrogel, carbon nanometer, patche, medicine delivery chip, and
Various nanocrystals, nano particle, nanogel, nanometer robot, micromodule equipment, microchip etc..Metal nanoparticle bag
Include the gold nanosphere with cavity researched and developed, gold nanorods etc..Although these drug delivery systems have been researched and developed and answered
With, but still suffer from the stability of carrier in vivo, interaction and security between cell or biological barrier etc.
A series of problems.It is always that people exert to improve drug effect, simplify application method, the drug powder of the attached Large Copacity of bag, reduce side effect
The direction of power.
By using stimulation modes such as pH, reduction-oxidation, enzyme, temperature, magnetic field, ultrasound, light, medicine can be delivered
And release.However, the external equipment of large volume needed for these stimulation modes and specialty.By electro photoluminescence reach medicine delivering and
Release, it is very simple, efficiently, and the parameter such as electric current, voltage is easily controllable, to reach accurate control drug dose, accurately
Reach the effect of point of drug release.
The content of the invention
In order to overcome the shortcoming of above-mentioned prior art, it is an object of the invention to provide a kind of liquid metal drug system and
It is prepared and delivering, method for releasing, using liquid metal as carrier, liquid metal and medicine is carried out a certain proportion of mixed
Close, be stirred continuously at low temperature, accelerate to generate new liquid metal oxide-film in air, while allowing medicine fully to stir with oxide-film
Contact is mixed, the cladding of liquid metal medicine is realized by the adhesiveness of liquid metal surface oxide-film, in different electric fields, profit
Delivering and the insoluble drug release of liquid metal medicine are carried out with electro photoluminescence；The liquid metal of coating medicine, with former liquid metal
Excellent properties, can convey, discharge medicine etc., can easily and fast, efficiently realize the delivering of liquid metal medicine and release
Put, be that liquid metal significantly expands application value in fields such as biomedical, pharmaceutical carrier delivering, future tumors treatments.
To achieve these goals, the technical solution adopted by the present invention is：
A kind of liquid metal drug system, including liquid metal and the medicine powder for being coated on liquid metal droplet outer surface
End.
The liquid metal is low-melting-point metal or alloy, and liquid metal is nanoscale, and particle diameter is preferably 100nm-
300nm, or size are less than normal cell.The drug powder is also nanoscale, and particle diameter is preferably 10nm-
100nm。
The liquid metal be gallium, indium, tin, bismuth, zinc, lead-containing alloy in one or more, or gallium, indium, tin, bismuth two
One or more in member, ternary or quaternary alloy；The drug powder is the drug substance for the treatment of cancer or tumour, including controls
Breast cancer, lung cancer, stomach cancer, oophoroma, liver cancer, advanced cancer, kinds cancer, the medicine of kinds of tumors are treated, for example：Treat mammary gland
Mycocet, PEG-PGlu micellas, taxol PEG-PAA micellas of cancer etc.；Treat the taxol PEG-PLA glue of lung cancer
Beam, Doxorubicin-HPMA etc.；Treat Doxorubicin pluronic micellas of stomach cancer etc.；Treat polyglutamic acid-purple of oophoroma
China fir alcohol etc.；Treat Doxorubicin-HPMA- galactosamines of liver cancer etc.；The docetaxel of the polypeptide targeting for the treatment of advanced cancer is received
Grain of rice etc.；Treat camptothecine-cyclodextrin of kinds cancer etc.；Treat Poly-L-glutamic acid-camptothecine of kinds of tumors etc..
The mass ratio of the liquid metal and drug powder is (5~10)：(0.5~1).Or other meet respective quality
The liquid metal and drug powder of ratio (preferably 10% or so).
Present invention also offers the preparation method of the liquid metal drug system, comprise the following steps：
S1：Raw material needed for preparing on demand；
S2：Liquid metal is added in glass beaker, the medicine of corresponding proportion is added, using agitator in a constant temperature
It is stirred under degree with certain rotating speed, liquid metal aoxidizes to form oxide-film in atmosphere, drug powder is coated on oxide-film；
S3：After the completion of to be mixed, wait for a period of time, the liquid metal and medicine after stirring are poured into another container
In, sealed, prevent the excessive ingress of air oxidation of liquid metal to be changed into not flow regime；
S4：The liquid metal of a part of coating medicine is taken out from sealing container, is put into HCl or NaOH solution,
The liquid metal for coating medicine keeps the spherical state that can arbitrarily move.
Described whipping temp is 30~60 DEG C, preferably 40 DEG C；The agitator be mechanical agitator, magnetic stirrer,
Ultrasonic stirrer or vibrations agitator, preferably ultrasonic vibration are stirred；The mixing time is 2~5 hours, preferably 2 hours.
In the S2, liquid metal droplet and medicine are subjected to fully shaking adhesion in microwave ultrasound device, make drug powder
The oxide-film to be formed load is aoxidized by liquid metal surface and is carried.
Present invention also offers the delivering of the liquid metal drug system, method for releasing, comprise the following steps：
S1：The liquid metal that medicine is coated is put into physiological solution, or Hank ' the s solution close with human body fluid composition,
Or in the low-down HCl solution of concentration, the liquid metal droplet that medicine is coated freely is moved in the solution；
S2：Fixed electrode is added at the two ends for the solution for being put into medicine cladding liquid metal, while applying voltage, the voltage
Size is less than the acceptable highest voltage 30V of human body, the liquid metal forward travel in the solution for enabling medicine to coat, and realizes
Delivering；
S3：The liquid metal of medicine cladding is contacted using negative electrode, electro photoluminescence is carried out, under certain voltage, realized
Insoluble drug release.
In the S3 or S4, voltage is 0~10V, preferably 10V；The fixed electrode can be by digital display DC voltage-stabilized power supply
PS-302D is provided；The distance of the medicine delivery can arbitrarily be selected according to the environment in human body；The speed of the insoluble drug release can
By adjusting, different voltage swings, physiological solution concentration are arbitrarily selected.
The theoretical foundation of the present invention is as follows：
Liquid metal (gallium indium eutectic alloy EGaIn), the metal of liquid is kept as a kind of peculiar property at room temperature, tool
There are high flexibility, deformability, high conductivity and nontoxicity, be widely used in all kinds of industrial circles and scientific circles field.Due to liquid
The deformability of state metal, flexible and miniaturization, make it have very big application prospect in nano-machines drug delivery system.
Liquid metal can arbitrarily prepare 100nm-300nm or more much smaller than normal cell due to deformability, plasticity
Size, can be used as pharmaceutical carrier, and in cell body and it is intravascular when running into barrier can also Free Transform pass through.Due to
The nontoxicity (in the solution of injection liquid metal, biological cell can also normal growth) of liquid metal, therefore also have good
Bio-compatibility.Because liquid metal essence is a kind of metal, therefore can also well it prevent by the immune system of human body
Cut and kill.
In terms of liquid metal is to the cladding of medicine, carrying and protection, due to liquid metal, surface can be formed in atmosphere
Layer oxide film, the film has accordion appearance and excellent adhesiveness, and various nano-metal particles, nano inorganic oxygen can be adhered
Compound, nanotube or nanometer powder etc..Therefore, also there is very big feasibility with liquid metal coating medicine, can fits
Cladding carrying for any medicine etc..
In terms of release of the liquid metal to medicine, experiment finds liquid metal after adhesion nano particle, in the solution
In the case of different voltage electro photoluminescence, the nano particle of the cladding can directly be discharged from liquid metal.Therefore, may be used
The medicine after loading is directly discharged by way of electro photoluminescence, this for the release of liquid metal medicine established good theory according to
According to.
In terms of transport of the liquid metal to medicine, because liquid metal can travel forward in the presence of electric field, and
Liquid metal after attached aluminium flake is gulped down can self-powered motion be up to several hours, this for liquid metal medicine delivery and conveying in terms of establish
Theoretical foundation is determined.
Compared with prior art, the beneficial effects of the invention are as follows：
1st, the delivering and release of the achievable liquid metal different pharmaceutical of the present invention, prepares the liquid gold of a variety of coating medicines
Category, this method is simple, conveniently, repeatable, and pollution-free, nonhazardous, environmental protection etc..
2nd, there is the liquid metal of coating medicine prepared by this method, liquid metal good carrying and protection to make to medicine
With.The liquid metal of coating medicine has all excellent properties of former liquid metal, can under electric field action in physiological solution or
Moved in the solution close with human body fluid composition and discharge load material, realize liquid metal medicine delivery and release.
Brief description of the drawings
Fig. 1 is a kind of flow chart of the preparation method of liquid metal coating medicine of the invention.
In figure：More drug adhesion is on liquid metal oxide-film surface, and quantity is more, and medicine is by liquid metal table
Bread covers very intensive.
Fig. 2 is the schematic diagram of liquid metal delivery process in human vas of coating medicine prepared by the present invention.
Fig. 3 is that the liquid metal of coating medicine prepared by the present invention treats the process of tumour or cancer cell in human body.
Reference：1 --- drug particles；2 --- liquid metal；3 --- the liquid metal of carrying medicament；4 --- blood
Pipe；5 --- red blood cell；6 --- tumour or cancer cell；A represents the release process of medicine.
Embodiment
Describe embodiments of the present invention in detail with reference to the accompanying drawings and examples.Following embodiment is used to illustrate this hair
It is bright, but it is not limited to the scope of the present invention.
Embodiment 1
Prepare liquid metal and drug substance：Liquid metal 2 is gallium-indium alloy Ga24.5In, drug substance includes how soft ratio
Star liposome, Doxorubicin-HPMA, Doxorubicin pluronic micellas, Doxorubicin-HPMA- galactosamines etc. are all kinds of.
Its preparation method, reference picture 1, comprises the following steps：
S1：Take liquid metal 2 --- gallium-indium alloy Ga24.5In and the Mycocet for the treatment of breast cancer etc., by 10g
Liquid metal 2 and 1g drug particles 1 are poured into different beakers respectively；
S2：Mixes liquid metal and treatment breast cancer medicines powder are stirred using magnetic stirrer, make liquid gold
More breast cancer medicines powder is adhered to after the constantly oxidation of the exocuticle of category, the rotating speed of stirring is 350r/min, and mixing time is
90min, whipping temp is 40 DEG C；
S3：After the completion of stirring, the liquid metal that the cladding prepared treats breast cancer medicines is moved into using suction pipe another
In container, sealing preserve；
S4：When needing to carry out breast cancer medicines delivering with the liquid metal, a drop cladding is taken out from the sealed container
The liquid metal of breast cancer medicines, is put into physiological solution or the solution close with human body fluid composition, makes the coating medicine
Liquid metal maintenance is spherical can flexible motion state；
S5:The liquid metal for loading different pharmaceutical prepares completion, i.e., the liquid metal 3 of carrying medicament in figure.
Embodiment 2
Medicine delivery and method for releasing in a kind of liquid metal for treating liver cancer, reference picture 2 and Fig. 3, comprise the following steps：
S1：Prepare the liquid metal of medicine cladding：Liquid metal is pure gallium Ga, and medicine is the nanoscale for the treatment of liver cancer
Grain.It is placed into certain density physiological solution or the solution close with human body fluid composition；
S2：The liquid metal bead of the miniature liver-cancer medicine cladding of a drop is taken, is placed on close with human body fluid composition
In Hank ' s solution, fixed electrode is added at the two ends of solution, while applying 10V voltages.The liquid metal for coating medicine
It can advance in the solution by certain speed, realize liquid metal medicine delivery, as shown in Fig. 2 in blood vessel 4, in the direction of the arrow
Move ahead, 5 be the red blood cell in blood；
S3：The liquid metal bead of the miniature cladding liver-cancer medicine of a drop is taken, is placed in Hank ' s solution, the one of solution
End adds fixed anode electrode, is placed on using negative electrode on the liquid metal bead that liver-cancer medicine is coated, and makes liquid gold
Category can slowly discharge liver-cancer medicine in the presence of electro photoluminescence, to realize liquid metal insoluble drug release, as shown in figure 3, releasing
Let off in journey A, drug particles 1 discharge from the liquid metal 3 of carrying medicament, act on tumour or cancer cell 6, realize medicine
Effect.
S4:The conveying and its release of liquid metal medicine are completed.
The better embodiment to this patent is explained in detail above, but this patent is not limited to above-mentioned embodiment party
, can also be on the premise of this patent objective not be departed from formula, the knowledge that one skilled in the relevant art possesses
Various changes can be made.
Claims (9)
1. a kind of liquid metal drug system, it is characterised in that including liquid metal and be coated on liquid metal droplet appearance
The drug powder in face.
2. liquid metal drug system according to claim 1, it is characterised in that the liquid metal be low-melting-point metal or
Alloy, liquid metal is nanoscale, and particle diameter is 100nm-300nm, or size is less than normal cell.The drug powder
Also it is nanoscale, particle diameter is 10nm-100nm.
3. liquid metal drug system according to claim 1, it is characterised in that the liquid metal be gallium, indium, tin, bismuth,
One or more in one or more in zinc, lead-containing alloy, or binary, ternary or the quaternary alloy of gallium, indium, tin, bismuth；Institute
State drug substance of the drug powder for treating cancer or tumour；The drug substance includes：Treat the Doxorubicin fat of breast cancer
Plastid, PEG-PGlu micellas, taxol PEG-PAA micellas；Treat the taxol PEG-PLA micellas of lung cancer, Doxorubicin-
HPMA；Treat the Doxorubicin pluronic micellas of stomach cancer；Treat polyglutamic acid-taxol of oophoroma；Treat liver cancer
Doxorubicin-HPMA- galactosamines；Treat the docetaxel nanometer grain of the polypeptide targeting of advanced cancer；Treat kinds cancer
Camptothecine-cyclodextrin；Treat Poly-L-glutamic acid-camptothecine of kinds of tumors.
4. liquid metal drug system according to claim 1, it is characterised in that the matter of the liquid metal and drug powder
Amount is than being (5~10)：(0.5~1).
5. the preparation method of liquid metal drug system described in claim 1, it is characterised in that comprise the following steps：
S1：Raw material needed for preparing on demand；
S2：Liquid metal is added in glass beaker, the medicine of corresponding proportion is added, using agitator at a certain temperature
It is stirred with certain rotating speed, liquid metal aoxidizes to form oxide-film in atmosphere, drug powder is coated on oxide-film；
S3：After the completion of to be mixed, wait for a period of time, the liquid metal and medicine after stirring are poured into another container, entered
Row sealing, prevents the excessive ingress of air oxidation of liquid metal to be changed into not flow regime；
S4：The liquid metal of a part of coating medicine is taken out from sealing container, is put into HCl or NaOH solution, makes medicine
The liquid metal of thing cladding keeps the spherical state that can arbitrarily move.
6. the preparation method of liquid metal drug system according to claim 5, it is characterised in that described whipping temp is
30~60 DEG C；The agitator is mechanical agitator, magnetic stirrer, ultrasonic stirrer or vibrations agitator；During the stirring
Between be 2~5 hours.
7. the preparation method of liquid metal drug system according to claim 5, it is characterised in that in the S2, by liquid
Molten drop and medicine carry out fully shaking adhesion in microwave ultrasound device, drug powder is aoxidized what is formed by liquid metal surface
Oxide-film is loaded and carried.
8. the delivering of liquid metal drug system, method for releasing described in claim 1, it is characterised in that comprise the following steps：
S1：The liquid metal that medicine is coated is put into physiological solution, or Hank ' the s solution close with human body fluid composition, or
In the low-down HCl solution of concentration, the liquid metal droplet that medicine is coated is set freely to move in the solution；
S2：Fixed electrode is added at the two ends for the solution for being put into medicine cladding liquid metal, while applying voltage, the voltage swing
Highest voltage 30V acceptable less than human body, the liquid metal forward travel in the solution for enabling medicine to coat, realization is passed
Send；
S3：The liquid metal of medicine cladding is contacted using negative electrode, electro photoluminescence is carried out, under certain voltage, realizes medicine
Release.
9. the delivering of liquid metal drug system, method for releasing described in claim 8, it is characterised in that electric in the S3 or S4
Press as 0~10V, the fixed electrode is provided by digital display DC voltage-stabilized power supply PS-302D.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108245495A (en) * | 2018-01-22 | 2018-07-06 | 云南靖创液态金属热控技术研发有限公司 | A kind of liquid metal pharmaceutical carrier and preparation method and application |
| CN108525128A (en) * | 2018-03-26 | 2018-09-14 | 清华大学 | Application of the liquid metal as tumour magnetic thermotherapy medium |
| CN108543070A (en) * | 2018-03-26 | 2018-09-18 | 清华大学 | A kind of load liquid state metal composite and its preparation method and application |
| CN108788124A (en) * | 2018-05-28 | 2018-11-13 | 北京梦之墨科技有限公司 | Micro-nano low-melting-point metal and preparation method thereof and electrically conductive ink and printing process |
| CN108994292A (en) * | 2018-09-18 | 2018-12-14 | 北京梦之墨科技有限公司 | A kind of method of modifying of low-melting-point metal |
| CN111760190A (en) * | 2020-06-30 | 2020-10-13 | 南方科技大学 | Degradable external stent and preparation method and application thereof |
| US10842550B2 (en) | 2017-10-13 | 2020-11-24 | Jen-Jie Chieh | Non-invasive thermal ablation device and method |
| CN114010782A (en) * | 2021-10-27 | 2022-02-08 | 清华大学 | Miniature drug-loaded robot based on magnetic liquid metal, preparation method and application method |
| CN114133273A (en) * | 2021-12-06 | 2022-03-04 | 湖北大学 | Preparation method of core-shell structure piezoelectric material and piezoelectric nano generator |
| RU2825245C1 (en) * | 2023-10-13 | 2024-08-22 | Федеральное государственное бюджетное учреждение науки Физический институт им. П.Н. Лебедева Российской академии наук (ФИАН) | Method of producing nanoparticles of bismuth with trigger ph-dependent transformation for biomedical applications |
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2017
- 2017-05-17 CN CN201710347292.XA patent/CN107137358A/en active Pending
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10842550B2 (en) | 2017-10-13 | 2020-11-24 | Jen-Jie Chieh | Non-invasive thermal ablation device and method |
| TWI711425B (en) * | 2017-10-13 | 2020-12-01 | 謝振傑 | Device for non-invasive thermal ablation |
| CN108245495A (en) * | 2018-01-22 | 2018-07-06 | 云南靖创液态金属热控技术研发有限公司 | A kind of liquid metal pharmaceutical carrier and preparation method and application |
| CN108525128A (en) * | 2018-03-26 | 2018-09-14 | 清华大学 | Application of the liquid metal as tumour magnetic thermotherapy medium |
| CN108543070A (en) * | 2018-03-26 | 2018-09-18 | 清华大学 | A kind of load liquid state metal composite and its preparation method and application |
| CN108788124A (en) * | 2018-05-28 | 2018-11-13 | 北京梦之墨科技有限公司 | Micro-nano low-melting-point metal and preparation method thereof and electrically conductive ink and printing process |
| CN108994292A (en) * | 2018-09-18 | 2018-12-14 | 北京梦之墨科技有限公司 | A kind of method of modifying of low-melting-point metal |
| CN111760190A (en) * | 2020-06-30 | 2020-10-13 | 南方科技大学 | Degradable external stent and preparation method and application thereof |
| CN111760190B (en) * | 2020-06-30 | 2024-06-07 | 南方科技大学 | Degradable external stent and preparation method and application thereof |
| CN114010782A (en) * | 2021-10-27 | 2022-02-08 | 清华大学 | Miniature drug-loaded robot based on magnetic liquid metal, preparation method and application method |
| CN114133273A (en) * | 2021-12-06 | 2022-03-04 | 湖北大学 | Preparation method of core-shell structure piezoelectric material and piezoelectric nano generator |
| RU2825245C1 (en) * | 2023-10-13 | 2024-08-22 | Федеральное государственное бюджетное учреждение науки Физический институт им. П.Н. Лебедева Российской академии наук (ФИАН) | Method of producing nanoparticles of bismuth with trigger ph-dependent transformation for biomedical applications |
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